CA2200942C - Organopolysiloxane compositions which can be crosslinked to give flame-resistant elastomers - Google Patents
Organopolysiloxane compositions which can be crosslinked to give flame-resistant elastomers Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The use is described of boron compounds chosen from the group consisting of boron carbide and metal borides mixed with non-reinforcing fillers, with the proviso that at least 75% by weight of the non-reinforcing fillers are heat-stable up to 1200°C, as flameproofing agents in organopolysiloxane compositions which can be crosslinked to flame-resistant elastomers.
Description
Docket: WA 9537-S
Paper No.1 ORGANOPOLYSILOXANE COMPOSITIONS WHICH CAN BE
CROSSLINKED TO GIVE FLAME-RESISTANT ELASTOMERS
BACKGROUND OF THE INVENTION
According to US 3,652,488 and the corresponding DE-C 20 34 919, flame resistance is obtained by addition of platinum and the flame-resistant to characteristic is enhanced by addition of carbon black As a result, these com-positions are naturally black The pale shades so often desired for joint sealing compositions cannot be produced.
US 3,821,140 and the corresponding DE-C 23 00 504 and US 3,677,999 describe flame-resistant or self~xtinguishing compositions which are pre-pared by addition of metal oxides or hydrates of metal oxides, such as hydra-ted aluminum oxide. At elevated temperatures in the course of a fire, water is split off from these products, and although this briefly reduces flammabil-ity, under the elevated temperatures which occur during a more prolonged fire it contributes toward destabilization of the dimethylpolysiloxane by 2 0 hydrolysis. On dissociation, basic oxides, such as magnesium oxide or alu-minum oxide, are formed from these hydrates of metal oxides, and intensify the decomposition under these conditions. The silicone matrix then disinte-grates completely due to depolymerization. Combinations of metal oxides/
hydrated metal oxides with graphite are known from US 4,405,425 and corre-2 5 sponding EP-B 40 750.
According to DE-B 29 09 462 and DE-A 30 41 031, flame-resistant polysiloxane compositions are prepared by addition of halogenat~ed diphenyl compounds, for example octabromodiphenyl ether. In the event of a fire however, polyhalogenated dibenzofurans or dibenzodioxins are formed from 3 0 these products, and these are undesirable because of the known toxicological problems. The use of these products might therefore be possible to only a limited extent in future.
None of the above mentioned methods lead to products which increase in volume in the event of a fire and thus show a so-called intumescence effect According to US 5,262,454 and corresponding DE-A 4013161 and US 4,694,030 and corresponding DE-A 36 02 888, this can be achieved by addition of expandable graphite compounds and other additives, such as nitrogen-containing polyphosphates, or by hollow glass beads. However, because of the presence of graphite, the products are black and no pale shades can be produced. Furthermore, the surfaces of the silicone composi-tions are rough and unattractive due to the addition of the expandable l0 graphite or the hollow glass beads, because these products are not available in the necessary small particle sizes (less than 20 Vim).
Boron compounds are used in silicone compositions because of their neutron-absorbing action. The use of boron carbide for this purpose is known from US 4,176,093.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to the use of boron compounds chosen from the group consisting of boron carbide and metal borides mixed with non-reinforcing fillers, with the proviso that at least 75~ by weight of the non-reinforcing fillers are heat-stable up to 1200°C, as flameproofing agents 2 0 in organopolysiloxane compositions which can be crosslinked to flame-resistant elastomers.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 is a graph plotting the results of examples 1 through 4, accord-ing to the invention and comparison examples 1 through 5. In figure 1 T is temperature in °C
t is duration of experiment in minutes is the theoretical temperature of the furnace -~ is examples 1, 2, 3 and 4 -!- is Comparison Experiments 1, 2, 3 and 5 3 0 -~- is Comparison Experiment 4 ~~aD ~~ ~.
DETAILED DF~~CRIPTION OF THE INVENTION
One object of the present invention was to provide organopolysiloxane compositions which can be crosslinked to flame-resistant elasfiomers and the disadvantages which occur in the prior art are avoided in the event of a fire.
A further object was to provide organopolysiloxane compositions which can be crosslinked to flame-resistant elastomers and in which the intrinsic color should be as light as possible, and with which elastomers are obtained which, in the event of a fire, increase their volume by foaming, where the foam should be as mechanically stable as possible, and should seal the joints as l0 tightly as possible and have a thermal insulation action which should delay an increase in temperature on the reverse of the component facing the fire for as long as possible. The object is achieved by the invention.
Examples of boron compounds are boron carbide, zinc boride, alumi-num boride, titanium boride and calcium boride.
One type of boron compound can be used , however it is possible to use a mixture of at least two boron compounds.
The predominant content of the non-reinforcing fillers having a spe-cific BET surface area of less than 50 m2/g, must be stable at the fire tempera-tures which usually occur, so that there is no decomposition with loss in vol-t 0 ume or a destabilization of the organopolysiloxane matrix owing to the for-oration of undesirable reaction products. Unsuitable fillers are calcium sul-fate and hydrated oxides of aluminum or magnesium, in which case undesir-able reaction products are water in the form of steam and also alkaline oxides, which are formed during the decomposition.
2 5 A content of calcium carbonate or calcium-magnesium carbonate, which split off carbon dioxide with a loss in volume, of up to 25% by weight of the total amount of non-reinforcing fillers is possible.
Preferably non-reinforcing fillers which are used are only those which are heat-stable up to 1200°C.
3 0 Examples of non-reinforcing fillers which are heat-stable up to 1200°C
are naturally occurring and synthetic silicon dioxides, such as diatomaceous earth, amorphous and crystalline quartres, silicates, such as mica, kaolin, L~~a~~~
tales and perlibes, silicatic fillers and naturally occurring and precipitated barium sulfafie. One type of filler can be used, however it is possible to use a mixture of at least two fillers.
As a result of the thermal decomposition of organopolysiloxane com-positions from a temperature of about 400°C, gaseous low molecular weight organosilicon compounds form, which lead to expansion of the silicone elas-tomers when they escape. Without the additions according to the invention, the organopolysiloxane matrix would decompose completely in the course of the fire. As a result of the additions according to the invention, a solid, foam-l0 like residue is formed. The silicon dioxide formed during thermal decom-position of the organopolysiloxane and the additions according to the inven-tion sinter to form a mechanically resistant foam. The low molecular weight compounds which form during decomposition of the organopolysiloxane act as blowing agents. Additional blowing agents are not necessary. In the event of a fire, this foam-like residue also shows an improved insulating action with respect to non-foaming joint compositions, and can be subjected to mechanical stress, in contrast to non-foaming joint compositions, which decompose to form a pulverulent residue which cannot be subjected to mechanical stress. A loss in volume and cracking in the remaining joint com-2 0 positions are avoided, so that no fire gases reach the reverse of the sealed-off structural components and spreading of the fire is therefore avoided.
The organopolysiloxane compositions which comprise the additions according to the invention include so-called condensation-crosslinking 1-component compositions and 2~omponent compositions and addition-crosslinking 2-component compositions based on organopolysiloxanes.
The organopolysiloxane compositions without the additions according to the invention are the same organopolysiloxane compositions which have been possible to use for the organopolysiloxane compositions known to date which can be crosslinked to flame-resistant elastomers.
3 o The organopolysiloxanes in the compositions according to the inven-tion can be any desired organopolysiloxanes which have been present in the ~~:~D 34 organopolysiloxane compositions known to date which can be crosslinked to flame-resistant elastomers.
The condensation-crosslinlung compositions are preferably organo-polysffoxanes which contain end groups which are capable of condensation, of the formula XRzSiO(RzSiO~"SiR?X ()]
in which R is identical or different, monovalent, optionally substitufied hydrocar-bon radicals having 1 to 18 carbon atoms per radical, X is a hydroxyl group and n is an integer of at least 10.
Optionally, all or some of the hydroxyl groups X in above mentioned formula (1) can be replaced by other groups which are capable of condensa-Lion, such as alkoxy groups having 1 to 4 carbon atoms per group.
The addition~rosslinking compositions are preferably organopolysi-loxanes which contain aliphatic carbon-carbon multiple bonds, of the formula YaRl3,Si0(R12Si0)b(R~YSiO)~iRl3.,Y, (In in which Rl is identical or different, monovalent, optionally substituted hvdrocar-2 0 bon radicals having 1 to 18 carbon atoms per radical, Y is a monovalent hydrocarbon radical with an aliphatic carbon~arbon multiple bond, preferably an alkenyl radical, more preferably a vinyl or hexenyl radical, and a is0orl, 2 5 b is an integer having a value from 20 to 10,000 and c is 0 or an integer having a value from 1 to 300.
In addition to the diorganosiloxane units RZSiO, other siloxane units can also be present within or along the siloxane chain of the organopolysilox-anes of the above mentioned formulae ()] and (In which is usually not shown 3 0 by such formulae. Examples of such other siloxane units, which are usually present only as an impurity, are those of the formulae RSi03~z, R~,SiOyz and Si04~z, where R has the meaning given above for this radical.
Paper No.1 ORGANOPOLYSILOXANE COMPOSITIONS WHICH CAN BE
CROSSLINKED TO GIVE FLAME-RESISTANT ELASTOMERS
BACKGROUND OF THE INVENTION
According to US 3,652,488 and the corresponding DE-C 20 34 919, flame resistance is obtained by addition of platinum and the flame-resistant to characteristic is enhanced by addition of carbon black As a result, these com-positions are naturally black The pale shades so often desired for joint sealing compositions cannot be produced.
US 3,821,140 and the corresponding DE-C 23 00 504 and US 3,677,999 describe flame-resistant or self~xtinguishing compositions which are pre-pared by addition of metal oxides or hydrates of metal oxides, such as hydra-ted aluminum oxide. At elevated temperatures in the course of a fire, water is split off from these products, and although this briefly reduces flammabil-ity, under the elevated temperatures which occur during a more prolonged fire it contributes toward destabilization of the dimethylpolysiloxane by 2 0 hydrolysis. On dissociation, basic oxides, such as magnesium oxide or alu-minum oxide, are formed from these hydrates of metal oxides, and intensify the decomposition under these conditions. The silicone matrix then disinte-grates completely due to depolymerization. Combinations of metal oxides/
hydrated metal oxides with graphite are known from US 4,405,425 and corre-2 5 sponding EP-B 40 750.
According to DE-B 29 09 462 and DE-A 30 41 031, flame-resistant polysiloxane compositions are prepared by addition of halogenat~ed diphenyl compounds, for example octabromodiphenyl ether. In the event of a fire however, polyhalogenated dibenzofurans or dibenzodioxins are formed from 3 0 these products, and these are undesirable because of the known toxicological problems. The use of these products might therefore be possible to only a limited extent in future.
None of the above mentioned methods lead to products which increase in volume in the event of a fire and thus show a so-called intumescence effect According to US 5,262,454 and corresponding DE-A 4013161 and US 4,694,030 and corresponding DE-A 36 02 888, this can be achieved by addition of expandable graphite compounds and other additives, such as nitrogen-containing polyphosphates, or by hollow glass beads. However, because of the presence of graphite, the products are black and no pale shades can be produced. Furthermore, the surfaces of the silicone composi-tions are rough and unattractive due to the addition of the expandable l0 graphite or the hollow glass beads, because these products are not available in the necessary small particle sizes (less than 20 Vim).
Boron compounds are used in silicone compositions because of their neutron-absorbing action. The use of boron carbide for this purpose is known from US 4,176,093.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to the use of boron compounds chosen from the group consisting of boron carbide and metal borides mixed with non-reinforcing fillers, with the proviso that at least 75~ by weight of the non-reinforcing fillers are heat-stable up to 1200°C, as flameproofing agents 2 0 in organopolysiloxane compositions which can be crosslinked to flame-resistant elastomers.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 is a graph plotting the results of examples 1 through 4, accord-ing to the invention and comparison examples 1 through 5. In figure 1 T is temperature in °C
t is duration of experiment in minutes is the theoretical temperature of the furnace -~ is examples 1, 2, 3 and 4 -!- is Comparison Experiments 1, 2, 3 and 5 3 0 -~- is Comparison Experiment 4 ~~aD ~~ ~.
DETAILED DF~~CRIPTION OF THE INVENTION
One object of the present invention was to provide organopolysiloxane compositions which can be crosslinked to flame-resistant elasfiomers and the disadvantages which occur in the prior art are avoided in the event of a fire.
A further object was to provide organopolysiloxane compositions which can be crosslinked to flame-resistant elastomers and in which the intrinsic color should be as light as possible, and with which elastomers are obtained which, in the event of a fire, increase their volume by foaming, where the foam should be as mechanically stable as possible, and should seal the joints as l0 tightly as possible and have a thermal insulation action which should delay an increase in temperature on the reverse of the component facing the fire for as long as possible. The object is achieved by the invention.
Examples of boron compounds are boron carbide, zinc boride, alumi-num boride, titanium boride and calcium boride.
One type of boron compound can be used , however it is possible to use a mixture of at least two boron compounds.
The predominant content of the non-reinforcing fillers having a spe-cific BET surface area of less than 50 m2/g, must be stable at the fire tempera-tures which usually occur, so that there is no decomposition with loss in vol-t 0 ume or a destabilization of the organopolysiloxane matrix owing to the for-oration of undesirable reaction products. Unsuitable fillers are calcium sul-fate and hydrated oxides of aluminum or magnesium, in which case undesir-able reaction products are water in the form of steam and also alkaline oxides, which are formed during the decomposition.
2 5 A content of calcium carbonate or calcium-magnesium carbonate, which split off carbon dioxide with a loss in volume, of up to 25% by weight of the total amount of non-reinforcing fillers is possible.
Preferably non-reinforcing fillers which are used are only those which are heat-stable up to 1200°C.
3 0 Examples of non-reinforcing fillers which are heat-stable up to 1200°C
are naturally occurring and synthetic silicon dioxides, such as diatomaceous earth, amorphous and crystalline quartres, silicates, such as mica, kaolin, L~~a~~~
tales and perlibes, silicatic fillers and naturally occurring and precipitated barium sulfafie. One type of filler can be used, however it is possible to use a mixture of at least two fillers.
As a result of the thermal decomposition of organopolysiloxane com-positions from a temperature of about 400°C, gaseous low molecular weight organosilicon compounds form, which lead to expansion of the silicone elas-tomers when they escape. Without the additions according to the invention, the organopolysiloxane matrix would decompose completely in the course of the fire. As a result of the additions according to the invention, a solid, foam-l0 like residue is formed. The silicon dioxide formed during thermal decom-position of the organopolysiloxane and the additions according to the inven-tion sinter to form a mechanically resistant foam. The low molecular weight compounds which form during decomposition of the organopolysiloxane act as blowing agents. Additional blowing agents are not necessary. In the event of a fire, this foam-like residue also shows an improved insulating action with respect to non-foaming joint compositions, and can be subjected to mechanical stress, in contrast to non-foaming joint compositions, which decompose to form a pulverulent residue which cannot be subjected to mechanical stress. A loss in volume and cracking in the remaining joint com-2 0 positions are avoided, so that no fire gases reach the reverse of the sealed-off structural components and spreading of the fire is therefore avoided.
The organopolysiloxane compositions which comprise the additions according to the invention include so-called condensation-crosslinking 1-component compositions and 2~omponent compositions and addition-crosslinking 2-component compositions based on organopolysiloxanes.
The organopolysiloxane compositions without the additions according to the invention are the same organopolysiloxane compositions which have been possible to use for the organopolysiloxane compositions known to date which can be crosslinked to flame-resistant elastomers.
3 o The organopolysiloxanes in the compositions according to the inven-tion can be any desired organopolysiloxanes which have been present in the ~~:~D 34 organopolysiloxane compositions known to date which can be crosslinked to flame-resistant elastomers.
The condensation-crosslinlung compositions are preferably organo-polysffoxanes which contain end groups which are capable of condensation, of the formula XRzSiO(RzSiO~"SiR?X ()]
in which R is identical or different, monovalent, optionally substitufied hydrocar-bon radicals having 1 to 18 carbon atoms per radical, X is a hydroxyl group and n is an integer of at least 10.
Optionally, all or some of the hydroxyl groups X in above mentioned formula (1) can be replaced by other groups which are capable of condensa-Lion, such as alkoxy groups having 1 to 4 carbon atoms per group.
The addition~rosslinking compositions are preferably organopolysi-loxanes which contain aliphatic carbon-carbon multiple bonds, of the formula YaRl3,Si0(R12Si0)b(R~YSiO)~iRl3.,Y, (In in which Rl is identical or different, monovalent, optionally substituted hvdrocar-2 0 bon radicals having 1 to 18 carbon atoms per radical, Y is a monovalent hydrocarbon radical with an aliphatic carbon~arbon multiple bond, preferably an alkenyl radical, more preferably a vinyl or hexenyl radical, and a is0orl, 2 5 b is an integer having a value from 20 to 10,000 and c is 0 or an integer having a value from 1 to 300.
In addition to the diorganosiloxane units RZSiO, other siloxane units can also be present within or along the siloxane chain of the organopolysilox-anes of the above mentioned formulae ()] and (In which is usually not shown 3 0 by such formulae. Examples of such other siloxane units, which are usually present only as an impurity, are those of the formulae RSi03~z, R~,SiOyz and Si04~z, where R has the meaning given above for this radical.
~.~~~94 One type of organopolysiloxane or several types of organopolyailox-anes cup be used.
The organopolysiloxanes have a viscosity of 1000 to 300,000 mPa-s at 25°C, preferably 6000 to 300,000 mPa.s at 25°C, and more preferably 20,000 to 300,000 mPa.s at 25°C
Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-P~PYI~ ~'P~PY~ n-butvl, iso-butyl, tart butyl, n-pentyl, iso-pentyi, neo-pentyl and Bert-pentyl radical; hexyl radicals, such as the n-hexyi radical;
heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl : adical and iso-octyl radicals, such as the 2,2,4-trimethylpentvl radical;
nonyl radicals, such as the n-nonvl radical; decyl radicals, such as the n-decyl radi-cal; dodecyl radicals, such as the n-dodecyl radical; and octadecyl radicals, such as the n-octadecyl radical; alkenyl radicals, such as the vinyl and the allyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cyclo-heptyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and g-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aral-kyl radicals, such as the benzyl radical and the a- and the 8-phenylethyl radi-cal 2 o Examples of substituted radicals R are cyanoalkyl radicals, such as the &cyanoethyi radical, and halogenated hydmarbon radicals, for example haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2~2,~,2',2'-hexafluoro-isoproPYl radical and the heptafluomisoproPYl radi-cal, and haloaryl radicals, such as the o-, m- and p-chlorophenyi radical.
2 5 With the exception of the alkenyl radicals, the examples of radicals R
also apply fio the radicals Rl. Examples of substi~ubed radicals R apply in their full scope to substituted radicals Rl.
Because of easier acxessibility alone, at least 50%, preferably at least 90%, of the number of radicals R and R~ in the organopolysiloxanes are pref s o erably methyl radicals.
The organopolysiloxanes have a viscosity of 1000 to 300,000 mPa-s at 25°C, preferably 6000 to 300,000 mPa.s at 25°C, and more preferably 20,000 to 300,000 mPa.s at 25°C
Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-P~PYI~ ~'P~PY~ n-butvl, iso-butyl, tart butyl, n-pentyl, iso-pentyi, neo-pentyl and Bert-pentyl radical; hexyl radicals, such as the n-hexyi radical;
heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl : adical and iso-octyl radicals, such as the 2,2,4-trimethylpentvl radical;
nonyl radicals, such as the n-nonvl radical; decyl radicals, such as the n-decyl radi-cal; dodecyl radicals, such as the n-dodecyl radical; and octadecyl radicals, such as the n-octadecyl radical; alkenyl radicals, such as the vinyl and the allyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cyclo-heptyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and g-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aral-kyl radicals, such as the benzyl radical and the a- and the 8-phenylethyl radi-cal 2 o Examples of substituted radicals R are cyanoalkyl radicals, such as the &cyanoethyi radical, and halogenated hydmarbon radicals, for example haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2~2,~,2',2'-hexafluoro-isoproPYl radical and the heptafluomisoproPYl radi-cal, and haloaryl radicals, such as the o-, m- and p-chlorophenyi radical.
2 5 With the exception of the alkenyl radicals, the examples of radicals R
also apply fio the radicals Rl. Examples of substi~ubed radicals R apply in their full scope to substituted radicals Rl.
Because of easier acxessibility alone, at least 50%, preferably at least 90%, of the number of radicals R and R~ in the organopolysiloxanes are pref s o erably methyl radicals.
~~o~~~ ~.
Crosslinking agents which are used for crosslinking the condensation-crosslinking organopolysiloxanes are preferably moisture-sensitive silanes of the formula RxSiZ~.x (II17 and/or partial hydrolysates thereof, which preferably contain 2 to 10 silicon atoms,in which R has the meaning given above, x is 0 or 1 and Z is identical or different hydrolyzable groups chosen from the group l0 consisting of acyloxy groups -OCORz optionally substituted hydroxycarbonoxy groups amino groups -NR~
oxime groups -0N=A
amide groups R40 _N-C_R2 aminoxy groups -O-NR~
2 0 enoxy groups -O-C=C-R~
i in which RZ is a monovalent hydrocarbon radical having 1 to 12 carbon atoms, R3 is a monovalent hydrocarbon radical having 1 to 4 carbon atoms, 2 5 R4 is hydrogen or identical or different, monovalent hydrocarbon radicals having 1 to 12 carbon atoms and A is identical or different radicals of the formula in which R5zC= or R6C=
3 0 R5 is identical or different, monovalent hydrocarbon radicals having 1 to 5 carbon atoms per radical and ~.~ao ~~ ~
R6 is a divalent hydrocarbon radical having 5 to 6 carbon atoms per radi-cal.
Examples of acyloxy groups are aceboxy and formyloxy groups and 2-ethyl-hexanoyloxy groups.
Examples of hydrocarbonoxy groups are methoxy, ethoxy, n-propy-foxy, isopropyloxy and n-butyloxy groups.
Examples of substituted hydrocarbonoxy groups are hydrocarbonoxy groups which are substitufied by alkoxy gmups, such as methoxyethylenoxy, ethoxyethylenoxy and methoxyisopropylenoxy gmups.
l0 Examples of amino groups are n-butylamino, sec-butylamino and cyclohexylamino groups.
Examples of oxime groups are methyl ethyl ketoxime groups, methyl isobutyl ketoxime groups, methyl n-amyl ketoxime groups and dimethyl ke-toxime groups.
Examples of amide groups are N-methylbenzamido groups and N-methyl-acetamido groups.
An example of an aminoxy group is the hydroxylamine group.
:fin example of an enoxv group is the isoprenoxy group.
For the crosslinking of condensation-crosslinking 2-component com-2 o positions, the hardener component is admixed immediately before use. This hardener component is preferably a tetraalkoxysilane, preferably tetraethyl or betrapropyl silicate.
Crosslinking catalysts which are used in the condensation-crosslinking 1- and 2~omponent compositions are the condensation catalysts known to the 2 5 expert Examples of condensation catalysts are butyl titanates and organic tin compounds, such as di-n-butyltin diacetabe, di-n-butyltin dilaurate and reac-lion products of a silane containing, per molecule, as hydrolyzable groups, at least two monovalent hydrocarbon radicals which are bonded to silicon via 3 o oxygen and are optionally substituted by an alkoxy group, or an oligomer thereof, with diorganotin diacylabe, all the valencies of the tin atoms in these reaction products being satisfied by oxygen atoms of the grouping ~Si06n~
or by SnC-bonded, monovalent organic radicals. The preparation of such reaction products is described in detail in US 4 460 761 (issued July 17,1984, A. Schiller et al., blacker-C'hemie GmbI~.
After application of the organopolysiloxane compositions, crosslinking to silicone elastomers takes place by access of atmospheric moisture.
In the case of addition-cmsslinking 2~omponent compositions, organopolysiloxanes containing Si-bonded hydrogen atoms are used as the crosslinking agent They are preferably of the formula 1 o HdR~..aSiO(R~SiO)e(RlHSiO)I,SiR~aHa in which Rl has the meaning given above, d is0orl, a is 0 or an integer having a value from 1 to 500 and f is an integer having a value from 1 to 200, with the proviso that on average at least 3 Si-bonded hydrogen atoms are present per molecule.
The hardener component is admixed immediately before use.
Crosslinking catalysts which are used in the case of addition crosslinking are platinum metals and/or compounds thereof, preferably platinum and/or compounds thereof. All the catalysts which have been used to date for addition of hydrogen atoms bonded directly to Si atoms onto aliphatically unsaturated compounds can be used. Examples of such catalysts are metallic and finely divided platinum, which can be on supports, such as 2 5 silicon dioxide, aluminum oxide or active charcoal, and compounds or com-plexes of platinum, such as platinum halides, for example PtC4, HzPtC~'6H.~0, NaiPtCl,'41-iz0, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, plati-num-aldehyde complexes, platinum-ketone complexes, including reaction 3 0 products of H2PtC16'6H20 and cyclohexanone, platinum-vinylsiloxane com-plexes, in particular platinum-divinylbetramethyldisiloxane complexes with or without a content of detectable organically bonded halogen, bis(gamma-~~Q'~~~~
picoline)platinum dichloride, trimethylene- dipyridineplatinum dichloride, dicyclopentadiene- platinum dichloride, dimethylsulfoxide-ethylene- plati-num(II) dichloride and reaction products of platinum tetrachloride with ole-fin and primary amine or secondary amine or primary and secondary amine, such as the reaction product of platinum tetrachloride, dissolved in 1-octane, with sec-butylamine, or ammonium-platinum complexes according to EP-B 110 370.
In addition to the organopolysiloxanes, crosslinking agents and crosslinking catalysts, the compositions according to the invention can optionally comprise further substances, such as reinforcing fillers, plasticiz-ers, such as dimethylpolysiloxanes or methylphenylpolysiloxanes which are blocked on the ends by trimethylsiloxy groups and have a viscosity of 10 to 5000 mPa-s at 25°C, preferably 35 to 1000 mPa~s at 25°C, adhesion pmmoters, such as organofunctional silanes or siloxanes, for example aminofunctional silanes or siloxanes, dispersing auxiliaries, pigments, fungicides and theological additives.
Examples of reinforcing fillers having a specific BET surface area of at least 50 mz/ g, are pyrogenically produced silicon dioxides and precipitated silicon dioxides. The reinforcing fillers, like the non-reinforcing fillers, can be 2 o hydmphobized by treatment with agents which render them hydrophobic, such as by treatment with st~earic acid or by treatment with organosilanes, -silazanes or -siloxanes. One type of filler can be used, but it is also possible to use a mixture of at least two fillers.
The organopolysiloxane compositions which comprise the additions 2 5 according to the invention are built up as follows:
(a) 10% to 80% by weight; preferably 20% to 70% by weight; of organo-polysiloxane which is capable of crosslanking (b) 0% to 40% by weight, preferably 10% to 30% by weight; of plasticizer which is not capable of crosslinking 30 (c) 0.5% bo 15% by weight, preferably 3% to 10% by weigh, of a~osslink-ing agent ?~ 0 (d) 0% to 50% by weight, preferably 3% to 10% by weigh, of reinforcing filler (e) 10% to 50% by weight, preferably 20% to 40% by weigh, of non-reinforcing filler (f) 0% to 10% by weight, preferably 1% to 3% by weight, of pigments (g) 0% to 2% by weigh, preferably 0.01% to 1.0% by weight, of catalyst (h) 0% to 10% by weight, preferably 0.1% to 3% by weight, of adhesion promoter and (i) 0.1% to 20% by weight, preferably 0.1% to 3% by weigh, of boron l0 compound, where the sum of the constituents must be 100% by weight.
The organopolysffoxane compositions according to the invention which can be crosslinked to flame-resistant elastomers can be used for all purposes for which organo-polysiloxanes which can be crosslinked to flame-resistant elastomers can be used, for example as joint-sealing compositions between structural components in structural and civil engineering, as a seal-ing composition for glazing and as sealing and embedding compositions for cable or pipe conduits through non-combustible building materials.
In the following examples, all percentage data relate to the weight 2 0 unless stated otherwise.
Example 1 The following constituents are brought together in succession in a suitable mixer.
30%of a,cu-dihydroxydimethylpolysiloxane, capable of crosslinking, viscosity of 80,000 mPa~s at 25°C
19.9% of plasticizer, dimethylpolysiloxane containing trimethylsiloxy groups, not capable of crosslinlcing, viscosity of 100 mPa~s at 25°C
6% of methyltrisbutanoneoximosilane as a crosslinking agent 3% of pyrogenic silicon dioxide acid having a specific surface area of 3 o about 150 m2/g, for example Wacker HDKT"" V 15 from Wacker-Chemie GmbH, Munich, as a reinforcing filler 38% of calcined kaolin, for example Lcecap K from Burgess Figment Company, USA, as a non-reinforcing filler 2% of Y-aminopropyltriethoxysilane as an adhesion promoter 1% of ground boron carbide fmm Elektroschmelzwerke Kempten GmbH, Munich, as an additive according to the invention 0.1 % of organotin catalyst for the crosslinking.
The finished composition is pale gray and can be colored in various desired shades, optionally, by suitable pigments. This non-sag consis-tency mixture is stored in commercially available cartridges with 1 o exclusion of moisture. The preferred use is sealing of vertical joints in buildings or ceiling joints into which the material is applied overhead.
For fire testing, the composition is introduced as a 12 x 12 mm wide and 500 mm long joint between 2 blocks of lightweight concrete with a circular cord of suitable material (for example closed-cell, foamed polyethylene, ceramic fibers or the like) as back-filling material, and is cured under standard climatic conditions. After initial storage for four weeks, the specimens are subjected to a burning test in a small burning furnace, such as is described in DIN 4102, part 8, in accordance with the standard burning curve according to DIN 4102, part 2 The tem-2 0 perature evolution in the burning space and on the reverse of the joint is recorded with 3 thermocouples. The temperatures on the reverse of the joint which are staffed in Table 1, and the values on which Figure 1 is based are the means of 2 measuring elements.
A temperature difference between the theoretical temperature of the 2 5 furnace space and the reverse of the joint is a measure of the thermal insulation action of the decomposed joint composition. The appear-ance of the joint and the consistency of the joint composition are evaluated after a burning test for 60 minutes. The results are stated in Table 1 and Figure 1.
3 o Comparison Experiment 1 The same constituents as in Example 1, but without bomn carbide, are mixed and subjected to testing.
Comparison Experiment 2 The same constituents as in Example 1, but with naturally occurring, ground calcium carbonate (OmyaT"" BLR3 from Omya, Cologne) instead of the aluminum silicate (calcined kaolin), are mixed and subjected to testing.
Comparison Experiment 3 The same constituents as in Comparison Experiment 2, but without boron carbide, are mixed and subjected to testing.
Comparison Experiment 4 l0 The same constituents as in Example 1, but with hydrated aluminum oxide treated with organosilane on the surface (MartinalT"~ OL from Martinswerke, Bergheim) instead of the aluminum silicafie (calcined kaolin), are mixed and subjected to testing.
Example 2 The following recipe constituents are brought together in succession in a suitable mixer:
66% of a,w-dihydroxydimethylsiloxane, capable of crosslinking, vis-cosity of 12,000 mPa~s at 25°C
33% of quartz flour, ground, for example Sicron SF 600 from 2 o Quarzwerke GmbH, Frechen as a non-reinforcing filler 1% of boron carbide analogous to Example 1.
This mixture is free-flowing and can be stored under normal condi-tions. Before use, 3% of a mixture of tetraethoxysilane and organotin catalyst is added for crosslinking and the components are mixed 2 5 intensively. Free-flowing mixtures are preferred for sealing horizontal wall openings. Preparation of the test specimens for the burning experiment and the burning test are carried out analogously to Exam-ple 1.
~. ~ a 9 ~. ~.
Example 3 The same constituents as in Example 2, but ground zirconium boride from Elektroschmelzwerke Kempten GmbH, Munich is used instead of boron carbide, are mixed and subjected to besting.
Example 4 The same constituents as in Example 2, but ground calcium boride from Elelctrnschmelzwerke IGempten GmbH, Munich, is used instead of boron carbide, are mixed and subjected to besting.
Comparison Experiment 5 The same constituents as in Example 2, but without boron carbide, are mixed and subjected to testing.
2~a~~4 2 Tabk 1 F.xpe~eat Evalnatlon Tempe~e Comyaenb after 60 a~abes aft 60 ssfa-ntd Example Joint perfect 331C Formation of a solid 1 foam-like material due to an mae~se in volume on the snrfsoe, no emergence of fire gees on the reverse of the ComparisonJoint has a 925C'') No incieese in voohzme, few aube-)~xperimenttraverse a~acks rial is soft, fire 1 gases emerge throe the cracks ComparisonJoint has many925C'~ Dea~eaee in volume due to de-Experimenttraverse a~aclcs composition, materirl 2 is soft, fire gases emerge th~ongh the a~~
ComparisonJoint has many925C") Decrease in volume due to de-Experimenttransverse rnmposition, material 3 arcs is very soft, fire gases emerge throngli the aaclcs ComparisonNo joint material925C") The joint material has deoom-Experimentremaining posed completely, 4 fire gases emerge througJi numerous cracks after about 35 minutes Example Joint perfect 335C Formatioax of a sabd 2 foamlihe material due to an ma~eoee in volume on the smrfaoe, no emu of fire gases on the reverse of the ' Example Joint perfect 342C Formation of a solid 3 foam-lilac material due to an i~aaeese in volume on the surface, no emu of fire gases on the reverse of the Example Joint perfect 338C Formation of a solid 4 foam-like material due to an is~a~ease in volume on the surface, no emergence of fire gases on the reverse of the ' Comparisonjoint has a 925C') No increase in vohime, few make-Experinnenttransverse rial is soft, fire asks gases emerge throe t~ cracks ') As a result of the transverse cracks which have occurred and the resulting emergence of the fire gases on the reverse of the joint during fire testing, the 5 theoretical temperature of the furnace interior and the reverse of the joint at the end of the experiment after 60 minutes are the same.
Crosslinking agents which are used for crosslinking the condensation-crosslinking organopolysiloxanes are preferably moisture-sensitive silanes of the formula RxSiZ~.x (II17 and/or partial hydrolysates thereof, which preferably contain 2 to 10 silicon atoms,in which R has the meaning given above, x is 0 or 1 and Z is identical or different hydrolyzable groups chosen from the group l0 consisting of acyloxy groups -OCORz optionally substituted hydroxycarbonoxy groups amino groups -NR~
oxime groups -0N=A
amide groups R40 _N-C_R2 aminoxy groups -O-NR~
2 0 enoxy groups -O-C=C-R~
i in which RZ is a monovalent hydrocarbon radical having 1 to 12 carbon atoms, R3 is a monovalent hydrocarbon radical having 1 to 4 carbon atoms, 2 5 R4 is hydrogen or identical or different, monovalent hydrocarbon radicals having 1 to 12 carbon atoms and A is identical or different radicals of the formula in which R5zC= or R6C=
3 0 R5 is identical or different, monovalent hydrocarbon radicals having 1 to 5 carbon atoms per radical and ~.~ao ~~ ~
R6 is a divalent hydrocarbon radical having 5 to 6 carbon atoms per radi-cal.
Examples of acyloxy groups are aceboxy and formyloxy groups and 2-ethyl-hexanoyloxy groups.
Examples of hydrocarbonoxy groups are methoxy, ethoxy, n-propy-foxy, isopropyloxy and n-butyloxy groups.
Examples of substituted hydrocarbonoxy groups are hydrocarbonoxy groups which are substitufied by alkoxy gmups, such as methoxyethylenoxy, ethoxyethylenoxy and methoxyisopropylenoxy gmups.
l0 Examples of amino groups are n-butylamino, sec-butylamino and cyclohexylamino groups.
Examples of oxime groups are methyl ethyl ketoxime groups, methyl isobutyl ketoxime groups, methyl n-amyl ketoxime groups and dimethyl ke-toxime groups.
Examples of amide groups are N-methylbenzamido groups and N-methyl-acetamido groups.
An example of an aminoxy group is the hydroxylamine group.
:fin example of an enoxv group is the isoprenoxy group.
For the crosslinking of condensation-crosslinking 2-component com-2 o positions, the hardener component is admixed immediately before use. This hardener component is preferably a tetraalkoxysilane, preferably tetraethyl or betrapropyl silicate.
Crosslinking catalysts which are used in the condensation-crosslinking 1- and 2~omponent compositions are the condensation catalysts known to the 2 5 expert Examples of condensation catalysts are butyl titanates and organic tin compounds, such as di-n-butyltin diacetabe, di-n-butyltin dilaurate and reac-lion products of a silane containing, per molecule, as hydrolyzable groups, at least two monovalent hydrocarbon radicals which are bonded to silicon via 3 o oxygen and are optionally substituted by an alkoxy group, or an oligomer thereof, with diorganotin diacylabe, all the valencies of the tin atoms in these reaction products being satisfied by oxygen atoms of the grouping ~Si06n~
or by SnC-bonded, monovalent organic radicals. The preparation of such reaction products is described in detail in US 4 460 761 (issued July 17,1984, A. Schiller et al., blacker-C'hemie GmbI~.
After application of the organopolysiloxane compositions, crosslinking to silicone elastomers takes place by access of atmospheric moisture.
In the case of addition-cmsslinking 2~omponent compositions, organopolysiloxanes containing Si-bonded hydrogen atoms are used as the crosslinking agent They are preferably of the formula 1 o HdR~..aSiO(R~SiO)e(RlHSiO)I,SiR~aHa in which Rl has the meaning given above, d is0orl, a is 0 or an integer having a value from 1 to 500 and f is an integer having a value from 1 to 200, with the proviso that on average at least 3 Si-bonded hydrogen atoms are present per molecule.
The hardener component is admixed immediately before use.
Crosslinking catalysts which are used in the case of addition crosslinking are platinum metals and/or compounds thereof, preferably platinum and/or compounds thereof. All the catalysts which have been used to date for addition of hydrogen atoms bonded directly to Si atoms onto aliphatically unsaturated compounds can be used. Examples of such catalysts are metallic and finely divided platinum, which can be on supports, such as 2 5 silicon dioxide, aluminum oxide or active charcoal, and compounds or com-plexes of platinum, such as platinum halides, for example PtC4, HzPtC~'6H.~0, NaiPtCl,'41-iz0, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, plati-num-aldehyde complexes, platinum-ketone complexes, including reaction 3 0 products of H2PtC16'6H20 and cyclohexanone, platinum-vinylsiloxane com-plexes, in particular platinum-divinylbetramethyldisiloxane complexes with or without a content of detectable organically bonded halogen, bis(gamma-~~Q'~~~~
picoline)platinum dichloride, trimethylene- dipyridineplatinum dichloride, dicyclopentadiene- platinum dichloride, dimethylsulfoxide-ethylene- plati-num(II) dichloride and reaction products of platinum tetrachloride with ole-fin and primary amine or secondary amine or primary and secondary amine, such as the reaction product of platinum tetrachloride, dissolved in 1-octane, with sec-butylamine, or ammonium-platinum complexes according to EP-B 110 370.
In addition to the organopolysiloxanes, crosslinking agents and crosslinking catalysts, the compositions according to the invention can optionally comprise further substances, such as reinforcing fillers, plasticiz-ers, such as dimethylpolysiloxanes or methylphenylpolysiloxanes which are blocked on the ends by trimethylsiloxy groups and have a viscosity of 10 to 5000 mPa-s at 25°C, preferably 35 to 1000 mPa~s at 25°C, adhesion pmmoters, such as organofunctional silanes or siloxanes, for example aminofunctional silanes or siloxanes, dispersing auxiliaries, pigments, fungicides and theological additives.
Examples of reinforcing fillers having a specific BET surface area of at least 50 mz/ g, are pyrogenically produced silicon dioxides and precipitated silicon dioxides. The reinforcing fillers, like the non-reinforcing fillers, can be 2 o hydmphobized by treatment with agents which render them hydrophobic, such as by treatment with st~earic acid or by treatment with organosilanes, -silazanes or -siloxanes. One type of filler can be used, but it is also possible to use a mixture of at least two fillers.
The organopolysiloxane compositions which comprise the additions 2 5 according to the invention are built up as follows:
(a) 10% to 80% by weight; preferably 20% to 70% by weight; of organo-polysiloxane which is capable of crosslanking (b) 0% to 40% by weight, preferably 10% to 30% by weight; of plasticizer which is not capable of crosslinking 30 (c) 0.5% bo 15% by weight, preferably 3% to 10% by weigh, of a~osslink-ing agent ?~ 0 (d) 0% to 50% by weight, preferably 3% to 10% by weigh, of reinforcing filler (e) 10% to 50% by weight, preferably 20% to 40% by weigh, of non-reinforcing filler (f) 0% to 10% by weight, preferably 1% to 3% by weight, of pigments (g) 0% to 2% by weigh, preferably 0.01% to 1.0% by weight, of catalyst (h) 0% to 10% by weight, preferably 0.1% to 3% by weight, of adhesion promoter and (i) 0.1% to 20% by weight, preferably 0.1% to 3% by weigh, of boron l0 compound, where the sum of the constituents must be 100% by weight.
The organopolysffoxane compositions according to the invention which can be crosslinked to flame-resistant elastomers can be used for all purposes for which organo-polysiloxanes which can be crosslinked to flame-resistant elastomers can be used, for example as joint-sealing compositions between structural components in structural and civil engineering, as a seal-ing composition for glazing and as sealing and embedding compositions for cable or pipe conduits through non-combustible building materials.
In the following examples, all percentage data relate to the weight 2 0 unless stated otherwise.
Example 1 The following constituents are brought together in succession in a suitable mixer.
30%of a,cu-dihydroxydimethylpolysiloxane, capable of crosslinking, viscosity of 80,000 mPa~s at 25°C
19.9% of plasticizer, dimethylpolysiloxane containing trimethylsiloxy groups, not capable of crosslinlcing, viscosity of 100 mPa~s at 25°C
6% of methyltrisbutanoneoximosilane as a crosslinking agent 3% of pyrogenic silicon dioxide acid having a specific surface area of 3 o about 150 m2/g, for example Wacker HDKT"" V 15 from Wacker-Chemie GmbH, Munich, as a reinforcing filler 38% of calcined kaolin, for example Lcecap K from Burgess Figment Company, USA, as a non-reinforcing filler 2% of Y-aminopropyltriethoxysilane as an adhesion promoter 1% of ground boron carbide fmm Elektroschmelzwerke Kempten GmbH, Munich, as an additive according to the invention 0.1 % of organotin catalyst for the crosslinking.
The finished composition is pale gray and can be colored in various desired shades, optionally, by suitable pigments. This non-sag consis-tency mixture is stored in commercially available cartridges with 1 o exclusion of moisture. The preferred use is sealing of vertical joints in buildings or ceiling joints into which the material is applied overhead.
For fire testing, the composition is introduced as a 12 x 12 mm wide and 500 mm long joint between 2 blocks of lightweight concrete with a circular cord of suitable material (for example closed-cell, foamed polyethylene, ceramic fibers or the like) as back-filling material, and is cured under standard climatic conditions. After initial storage for four weeks, the specimens are subjected to a burning test in a small burning furnace, such as is described in DIN 4102, part 8, in accordance with the standard burning curve according to DIN 4102, part 2 The tem-2 0 perature evolution in the burning space and on the reverse of the joint is recorded with 3 thermocouples. The temperatures on the reverse of the joint which are staffed in Table 1, and the values on which Figure 1 is based are the means of 2 measuring elements.
A temperature difference between the theoretical temperature of the 2 5 furnace space and the reverse of the joint is a measure of the thermal insulation action of the decomposed joint composition. The appear-ance of the joint and the consistency of the joint composition are evaluated after a burning test for 60 minutes. The results are stated in Table 1 and Figure 1.
3 o Comparison Experiment 1 The same constituents as in Example 1, but without bomn carbide, are mixed and subjected to testing.
Comparison Experiment 2 The same constituents as in Example 1, but with naturally occurring, ground calcium carbonate (OmyaT"" BLR3 from Omya, Cologne) instead of the aluminum silicate (calcined kaolin), are mixed and subjected to testing.
Comparison Experiment 3 The same constituents as in Comparison Experiment 2, but without boron carbide, are mixed and subjected to testing.
Comparison Experiment 4 l0 The same constituents as in Example 1, but with hydrated aluminum oxide treated with organosilane on the surface (MartinalT"~ OL from Martinswerke, Bergheim) instead of the aluminum silicafie (calcined kaolin), are mixed and subjected to testing.
Example 2 The following recipe constituents are brought together in succession in a suitable mixer:
66% of a,w-dihydroxydimethylsiloxane, capable of crosslinking, vis-cosity of 12,000 mPa~s at 25°C
33% of quartz flour, ground, for example Sicron SF 600 from 2 o Quarzwerke GmbH, Frechen as a non-reinforcing filler 1% of boron carbide analogous to Example 1.
This mixture is free-flowing and can be stored under normal condi-tions. Before use, 3% of a mixture of tetraethoxysilane and organotin catalyst is added for crosslinking and the components are mixed 2 5 intensively. Free-flowing mixtures are preferred for sealing horizontal wall openings. Preparation of the test specimens for the burning experiment and the burning test are carried out analogously to Exam-ple 1.
~. ~ a 9 ~. ~.
Example 3 The same constituents as in Example 2, but ground zirconium boride from Elektroschmelzwerke Kempten GmbH, Munich is used instead of boron carbide, are mixed and subjected to besting.
Example 4 The same constituents as in Example 2, but ground calcium boride from Elelctrnschmelzwerke IGempten GmbH, Munich, is used instead of boron carbide, are mixed and subjected to besting.
Comparison Experiment 5 The same constituents as in Example 2, but without boron carbide, are mixed and subjected to testing.
2~a~~4 2 Tabk 1 F.xpe~eat Evalnatlon Tempe~e Comyaenb after 60 a~abes aft 60 ssfa-ntd Example Joint perfect 331C Formation of a solid 1 foam-like material due to an mae~se in volume on the snrfsoe, no emergence of fire gees on the reverse of the ComparisonJoint has a 925C'') No incieese in voohzme, few aube-)~xperimenttraverse a~acks rial is soft, fire 1 gases emerge throe the cracks ComparisonJoint has many925C'~ Dea~eaee in volume due to de-Experimenttraverse a~aclcs composition, materirl 2 is soft, fire gases emerge th~ongh the a~~
ComparisonJoint has many925C") Decrease in volume due to de-Experimenttransverse rnmposition, material 3 arcs is very soft, fire gases emerge throngli the aaclcs ComparisonNo joint material925C") The joint material has deoom-Experimentremaining posed completely, 4 fire gases emerge througJi numerous cracks after about 35 minutes Example Joint perfect 335C Formatioax of a sabd 2 foamlihe material due to an ma~eoee in volume on the smrfaoe, no emu of fire gases on the reverse of the ' Example Joint perfect 342C Formation of a solid 3 foam-lilac material due to an i~aaeese in volume on the surface, no emu of fire gases on the reverse of the Example Joint perfect 338C Formation of a solid 4 foam-like material due to an is~a~ease in volume on the surface, no emergence of fire gases on the reverse of the ' Comparisonjoint has a 925C') No increase in vohime, few make-Experinnenttransverse rial is soft, fire asks gases emerge throe t~ cracks ') As a result of the transverse cracks which have occurred and the resulting emergence of the fire gases on the reverse of the joint during fire testing, the 5 theoretical temperature of the furnace interior and the reverse of the joint at the end of the experiment after 60 minutes are the same.
Claims (6)
1. A method for preparing organopolysiloxane compositions which when crosslinked form flame-resistant elastomers comprising:
adding a boron compound chosen from the group consisting of boron carbide and a metal boride which is mixed with a non-reinforcing filler to the organopolysiloxane which is crosslinkable to form elastomers, with the proviso that at least 75% by weight of the non-reinforcing filler is heat-stable at temperatures of up to 1200°C, wherein the boron compound is present in an amount of 0.1 % to 20% by weight, based on the total weight of the organopolysiloxane composition which is crosslinkable to form elastomers.
adding a boron compound chosen from the group consisting of boron carbide and a metal boride which is mixed with a non-reinforcing filler to the organopolysiloxane which is crosslinkable to form elastomers, with the proviso that at least 75% by weight of the non-reinforcing filler is heat-stable at temperatures of up to 1200°C, wherein the boron compound is present in an amount of 0.1 % to 20% by weight, based on the total weight of the organopolysiloxane composition which is crosslinkable to form elastomers.
2. The method as claimed in claim 1, wherein the boron compound is chosen from the group consisting of boron carbide, zinc boride, alumi-num boride, titanium boride and calcium boride.
3. The method as claimed in claim 1, wherein the non-reinforcing filler, which is stable up to 1200°C, is chosen from the group consisting of naturally occurring and synthetic silicon dioxides, amorphous and crystalline quartzes, silicates, silicatic fillers and naturally occurring and precipitated barium sulfates.
4. The method as claimed in claim 1, wherein the boron compound is present in an amount of 0.1 % to 3% by weight, based on the total weight of the organopolysiloxane composition with is crosslinkable to form elastomers.
5. The method as claimed in claim 1, wherein the non-reinforcing filler is present in an amount of 10% to 50% by weight, based on the total weight of organopolysiloxane composition which is crosslinkable to form elasbomers.
6. A flame-resistant elastomer, consisting of the reaction product of;
(a) 10% to 80% by weight of an organopolysiloxane which is capable of crosslinking, (b) 0% to 40% by weight of a plasticizer which is not capable of crosslink-mg, (c) 0.5% to 15% by weight of a crosslinking agent, (d) 0% to 50% by weight of a reinforcing filler (e) 10% to 50% by weight of a non-reinforcing filler, which is heat stable up to 1200°C.
(f) 0% to 10% by weight of a pigment, (g) 0% to 2% by weight of a catalyst capable of promoting crosslinking, (h) 0% to 10% by weight of an adhesion promoter and (i) 0.1% to 20% by weight of a boron compound selected from the group consisting of boron carbide and a metal boride.
(a) 10% to 80% by weight of an organopolysiloxane which is capable of crosslinking, (b) 0% to 40% by weight of a plasticizer which is not capable of crosslink-mg, (c) 0.5% to 15% by weight of a crosslinking agent, (d) 0% to 50% by weight of a reinforcing filler (e) 10% to 50% by weight of a non-reinforcing filler, which is heat stable up to 1200°C.
(f) 0% to 10% by weight of a pigment, (g) 0% to 2% by weight of a catalyst capable of promoting crosslinking, (h) 0% to 10% by weight of an adhesion promoter and (i) 0.1% to 20% by weight of a boron compound selected from the group consisting of boron carbide and a metal boride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19620816.5 | 1996-05-23 | ||
| DE19620816A DE19620816A1 (en) | 1996-05-23 | 1996-05-23 | Crosslinkable organopolysiloxane compositions to be flame-resistant elastomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2200942A1 CA2200942A1 (en) | 1997-11-23 |
| CA2200942C true CA2200942C (en) | 2002-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002200942A Expired - Fee Related CA2200942C (en) | 1996-05-23 | 1997-03-25 | Organopolysiloxane compositions which can be crosslinked to give flame-resistant elastomers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5922799A (en) |
| EP (1) | EP0808867A1 (en) |
| JP (1) | JPH1081823A (en) |
| KR (1) | KR100235543B1 (en) |
| CA (1) | CA2200942C (en) |
| DE (1) | DE19620816A1 (en) |
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| JP2000309708A (en) * | 1999-04-26 | 2000-11-07 | Kanegafuchi Chem Ind Co Ltd | Curable resin composition and foamable resin composition |
| EP1113048A3 (en) | 1999-12-27 | 2002-01-30 | General Electric Company | Hydrophobicity imparting particulate |
| US20070190872A1 (en) * | 2006-02-16 | 2007-08-16 | Weber Robert F | Fire retardant silicone textile coating |
| FR2899905B1 (en) * | 2006-04-12 | 2008-07-18 | Rhodia Recherches & Tech | HOT VULCANIZABLE POLYORGANOSILOXANE COMPOSITIONS USEFULLY USEFUL FOR THE MANUFACTURE OF ELECTRIC WIRES OR CABLES |
| FR2907787B1 (en) * | 2006-10-31 | 2010-05-21 | Sncf | SILICONE FOAM ADDITIONED THERMAL AGENT AND USES OF THE FOAM |
| CN102220008B (en) * | 2011-05-10 | 2012-08-15 | 嘉兴多角电线电缆有限公司 | High-intensity fire-proof cable insulating material and preparation method of high-intensity fire-proof cable insulating material |
| FR2987367B1 (en) * | 2012-02-28 | 2015-03-06 | Commissariat Energie Atomique | FIRE PROTECTIVE MATERIAL, HIGH PRESSURE STORAGE TANK COATED WITH SUCH MATERIAL, PROCESSES FOR THEIR PREPARATION AND USES THEREOF |
| WO2020231603A1 (en) | 2019-05-16 | 2020-11-19 | Dow Global Technologies Llc | Compatibilized blends of terephalate ester polyols and hydrocarbon blowing agents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652488A (en) * | 1969-07-16 | 1972-03-28 | Dow Corning | Flame resistant silicone elastomers containing carbon black and platinum |
| DE1955524C2 (en) * | 1969-11-05 | 1980-10-02 | Siemens Ag, Berlin Und Muenchen, 8000 Muenchen | Cast resin molding compounds for the production of non-combustible electrical components |
| BE793729A (en) * | 1972-01-07 | 1973-07-05 | Rhone Poulenc Sa | ORGANOPOLYSILOXANIC COMPOSITIONS |
| JPS5145145A (en) * | 1974-10-16 | 1976-04-17 | Ig Gijutsu Kenkyusho Kk | Taika tainetsusei ojusuru goseijushi |
| US4176093A (en) * | 1977-02-22 | 1979-11-27 | Zoch Harold L | Neutron absorbing room temperature vulcanizable silicone rubber compositions |
| DE2909462C3 (en) * | 1979-03-10 | 1982-04-15 | Perennatorwerk Alfred Hagen Gmbh, 6200 Wiesbaden | Flameproofing of polyorganosiloxane compositions |
| DE3018549A1 (en) * | 1980-05-14 | 1981-11-19 | Wacker-Chemie GmbH, 8000 München | FOR FLAME REPELLENT ELASTOMERS, IF ANY AFTER THE ADDITION OF CROSSLINKING AGENTS, CROSSLINKABLE SIZES BASED ON ORGANOPOLYSILOXANE |
| DE3041031A1 (en) * | 1980-10-31 | 1982-06-09 | Perennatorwerk Alfred Hagen Gmbh, 6200 Wiesbaden | Flameproofing hardenable or hardened poly-organo-siloxane! elastomer - with powdered mixt. contg. chalk, halogenated di:phenyl deriv(s) and opt. antimony tri:oxide |
| DE3212008A1 (en) * | 1982-03-31 | 1983-10-06 | Wacker Chemie Gmbh | EXCLUDING WATER STORAGE CROSS-LINKABLE DIMENSIONS WHEN THE WATER ACCESSES AT ROOM TEMPERATURE |
| AU1910783A (en) * | 1982-11-29 | 1984-06-07 | Sws Silicones Corp. | Organopolysiloxane composition |
| US4433069A (en) * | 1983-01-03 | 1984-02-21 | Dow Corning Corporation | Method for preparing flame resistant polysiloxane foams and foams prepared thereby |
| DE3602888A1 (en) * | 1986-01-31 | 1987-08-06 | Bayer Ag | INTUMESCENT POLYSILOXANE MOLDS |
| DE4013161A1 (en) * | 1990-04-25 | 1991-11-07 | Schott Glaswerke | FLAME RESISTANT POLYORGANOSILOXANE |
| US5262454A (en) * | 1990-04-25 | 1993-11-16 | Down Corning Gmbh | Flame-resistant polyorganosiloxane compound containing hollow glass balls and intumescent compound |
| US5401793A (en) * | 1991-03-20 | 1995-03-28 | Dainippon Ink And Chemicals, Inc. | Intumescent fire-resistant coating, fire-resistant material, and process for producing the fire-resistant material |
| DE69223550T2 (en) * | 1991-05-28 | 1998-04-16 | Denki Kagaku Kogyo Kk | Flame retardant resin composition |
-
1996
- 1996-05-23 DE DE19620816A patent/DE19620816A1/en not_active Withdrawn
-
1997
- 1997-02-24 US US08/805,088 patent/US5922799A/en not_active Expired - Fee Related
- 1997-03-25 CA CA002200942A patent/CA2200942C/en not_active Expired - Fee Related
- 1997-05-22 JP JP9132222A patent/JPH1081823A/en active Pending
- 1997-05-22 EP EP97108281A patent/EP0808867A1/en not_active Withdrawn
- 1997-05-22 KR KR1019970020105A patent/KR100235543B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1081823A (en) | 1998-03-31 |
| DE19620816A1 (en) | 1997-11-27 |
| KR970074841A (en) | 1997-12-10 |
| CA2200942A1 (en) | 1997-11-23 |
| EP0808867A1 (en) | 1997-11-26 |
| KR100235543B1 (en) | 1999-12-15 |
| US5922799A (en) | 1999-07-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |